EP0640571A1 - Vitro-céramique transformant de longueur d'ondes de la lumière et son procédé de production - Google Patents
Vitro-céramique transformant de longueur d'ondes de la lumière et son procédé de production Download PDFInfo
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- EP0640571A1 EP0640571A1 EP94306307A EP94306307A EP0640571A1 EP 0640571 A1 EP0640571 A1 EP 0640571A1 EP 94306307 A EP94306307 A EP 94306307A EP 94306307 A EP94306307 A EP 94306307A EP 0640571 A1 EP0640571 A1 EP 0640571A1
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- glass
- rare earth
- fluoride
- earth ions
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- 238000000034 method Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 title abstract description 18
- 239000002241 glass-ceramic Substances 0.000 title description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 26
- -1 rare earth ions Chemical class 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006112 glass ceramic composition Substances 0.000 claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000005383 fluoride glass Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000007496 glass forming Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000004031 devitrification Methods 0.000 claims description 2
- 230000003467 diminishing effect Effects 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims 1
- 230000005284 excitation Effects 0.000 description 11
- 238000000295 emission spectrum Methods 0.000 description 7
- 150000002222 fluorine compounds Chemical class 0.000 description 7
- 229910009520 YbF3 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000075 oxide glass Substances 0.000 description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- 229910016495 ErF3 Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- QGJSAGBHFTXOTM-UHFFFAOYSA-K trifluoroerbium Chemical compound F[Er](F)F QGJSAGBHFTXOTM-UHFFFAOYSA-K 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910008903 TmF3 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/17—Solid materials amorphous, e.g. glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/09—Processes or apparatus for excitation, e.g. pumping
- H01S3/091—Processes or apparatus for excitation, e.g. pumping using optical pumping
- H01S3/094—Processes or apparatus for excitation, e.g. pumping using optical pumping by coherent light
- H01S3/094092—Upconversion pumping
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/1601—Solid materials characterised by an active (lasing) ion
- H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
Definitions
- This invention relates to a high efficiency wavelength up-conversion transparent glass ceramic composition containing rare earth ions, which can be applied for example to short wavelength solid lasers, full color displays and infrared light detecting sensors, and a process for the production thereof.
- wavelength up-conversion materials utilizing the electronic transition between a plurality of energy levels of rare earth ions have been studied with keen interest because they can be applied in various fields such as blue or green solid lasers, full color displays and infrared light detecting sensors.
- fluoride single crystals and glasses have hitherto been known.
- fluoride glass in the form of a fiber is capable of effectively sealing an excitation light in a fiber core, a visible light fiber laser having the highest infrared conversion efficiency has been obtained at the present time.
- fluoride glass is inferior to the fluoride single crystal in thermal, mechanical and chemical stability and has problems in durability and reliability, for example.
- fluoride glass tends to deteriorate by erosion with water and when subjected to irradiation bya laser beam of large power, it is very prone to be damaged.
- precise control of the preparation conditions such as temperature and atmosphere, is essential thus resulting in increase of production cost.
- a glass having a very high stability is known a composition, typical of optical glasses, comprising, as a predominant component, oxides.
- Ordinary optical glasses containing the so-called glass-forming materials having very high chemical bonding strength, such as SiO2, GeO2, AlO 1.5 , BO 1.5 , PO 2.5 exhibit high viscosity and are much more superior in moldability, water resistance, and mechanical strength, than fluoride glasses containing ionic bonding compounds.
- oxide glasses however, the emission efficiency from a number of rare earth ion levels is significantly lower than that of fluorides, and oxide glasses are not suitable for use as applying devices utilizing emission of rare earth ions, for example, laser materials.
- glass consisting of high quality fluoride meets with higher production cost and oxide glass with high stability meets with lower emission efficiency.
- a transparent glass ceramic composition having the following chemical composition, in which fluoride fine crystals containing rare earth ions are preferentially precipitated:
- Fig. 1 is an example of emission spectra when Example 1 of the infrared-to-visible up-conversion material of the present invention is excited by an infrared light of wavelength 980 nm [(a) before heat treatment, (b) after heat treatment and (c) Er-Yb added fluoride glass according to Comparative Example 1].
- Fig. 2 shows scattering curves of the material of Example 1 (a) before heat treatment and (b) after heat treatment.
- Fig. 3 shows transmission spectra of the material of Example 1 (a) before heat treatment and (b) after heat treatment.
- Fig. 4 shows the excitation power dependence of the emission intensity of the glass ceramic and fluoride glass according to Example 1 and Comparative Example 1.
- Fig. 5 shows visible light emission spectra when (a) the material of Example 2 and (b) Tm3+ - and Yb3+ -added fluoride glass are excited by an infrared light of wavelength 980 nm.
- the inventors have made various efforts to develop a high efficiency wavelength up-conversion transparent glass ceramic composition containing rare earth ions to be applied to short wavelength solid lasers, full color displays and infrared light detecting sensors and have discovered the transparent glass ceramic composition having the foregoing chemical composition, in which fluoride fine crystals containing rare earth ions are preferentially precipitated.
- SiO2 and AlO 1.5 or GaO 1.5 are important as glass raw materials for forming the network structure of the transparent glass matrix and with increase of the content of SiO2, the glass tends to be formed, but desired fluoride fine crystals are difficult to precipitate.
- SiO2 is at least 60 mol % or AlO 1.5 or GaO 1.5 is at least 40 mol %, the fine crystals cannot be precipitated and the emission efficiency is decreased.
- PbF2 and CdF2 not only promote formation of the glass, but also play an essential role in precipitating the fine crystals. When more than 60 mol % of PbF2 and CdF2 are added, a glass is not formed.
- GeO2 is a component playing the same role as SiO2 and even when a part of SiO2 is replaced by GeO2,the formation of the glass is not affected.
- TiO2 or ZrO2 is effective for the precipitation of the fine crystals even if added in a small amount and when adding at least 10 mol %, this component is not dissolved.
- Rare earth elements (Re +3) are emission components, of which Yb +3 as a sensitizer is preferably used in a larger amount, e.g. about 20 mol % and other Re3+ elements are preferably used in an amount of up to 5 mol % so as to prevent concentration quenching.
- a process for the production of a transparent glass ceramic composition comprising preparing an oxidefluoride glass containing rare earth ions by a conventional melting method, subjecting the glass to a heat treatment at a temperature higher than the glass transition temperature and thereby precipitating preferentially fluoride fine crystals containing a large amount of rare earth ions.
- glass-forming materials for example, powders of SiO2, AlO 1.5 and fluorides such as PbF2, CdF2, ReF3 (rare earth element fluorides) are mixed, charged to a platinum crucible, solubilized in the air at a temperature of about 1000 °C, cast in a mold of carbon and charged to an annealing furnace to remove the strain.
- GeO2 or BO 1.5 can be used as a raw material or raw component instead of SiO2; GaO 1.5 or TiO2 instead of AlO 1.5 and rare earth oxides ReO 1.5 instead of the rare earth fluorides ReF3.
- the important point is to stably incorporate fluorides into an oxide glass, subjecting the mixture to a heat treatment and thereby precipitating fluoride fine crystals containing rare earth ions.
- Heavy metal fluorides such as PbF2, CdF2, TlF, etc. are preferable as the component, since they metastably form ionic bonds with fluoride ion in the oxide glass network and function to prevent the rare earth ions from direct bonding with Si-O.
- the atmosphere used for melting the glass is not limited, but can be air.
- crucibles there can be used crucibles of platinum, alumina, or silica.
- Powders of oxides and fluorides as raw materials are mixed, charged to a platinum crucible provided with a cover and uniformly melted at about 1000 °C.
- the content of AlO 1.5 , TiO2 or ZrO2 each having a high melting point is larger, it is preferable to adjust the melting temperature somewhat higher (less than 1200 °C). If the temperature is higher than 1200 °C, however, a loss of the fluoride due to evaporation is so increased that the melt should be prevented from reaching such a high temperature.
- the melting time depending upon the amount of one batch, is generally 1 to 2 hours in the case of about 100 g, and with the increase of the amount thereof, the melting time is preferably lengthened to homogenize the mixture. However, the maintenance of the melt for a longer period of time should be avoided since the loss of fluorides due to evaporation is significant.
- the glass melt is cast in a mold, solidified, annealed near the glass transition temperature (Tg), cooled therefrom to a temperature of about 50 °C lower than Tg, further heated and heat-treated at a temperature of about 100 °C higher than Tg and thus fine crystals are precipitated.
- Tg glass transition temperature
- the heat treatment temperature is different according to the glass composition. As long as denitrification does not occur, it is preferable to effect the heat treatment at a higher temperature from the standpoint of efficiency and at a higher temperature the heat treatment time is shorter, but in general, the heat treatment should preferably be carried out for at least 10 hours.
- Powders of SiO2, Al(OH)3, PbF2, CdF2, YbF3 and ErF3 were weighed and mixed to give a composition of 30 % SiO2, 15 % AlO 1.5 , 24 % PbF2, 20% CdF2, 10 % YbF3 and 1 % ErF3 (mol %).
- the resulting mixture was charged to a platinum crucible and melted for about 1 hour in air at a temperature of 1050 °C.
- the unifomly melted mixture was cast in a mold of carbon and annealed at 400 °C.
- the thus obtained transparent glass was further heat treated at a temperature of 470 °C for 7 hours and alowed to stand and cool at room temperature.
- Fig. 1 shows emission spectra when (a) the glass free from the heat treatment and (b) the same glass but heat-treated at 470 °C are irradiated by a semiconductor laser with a wavelength of 980 nm.
- the emissions at a wavelength band of 550 nm and 660 nm are respectively green and red emission by Er 3+ and in particular, the emission of 550 nm is expected to be applied to short wavelength lasers and the like. It is apparent from Fig. 1 that the emission intensity in the visible range is improved by at least about 100 times by the heat treatment at 470 °C.
- Fig. 2 shows X-ray scattering curves of the samples before and after the heat treatment in this Example. It is shown therein that the sample before the heat treatment (a) gives a broad curve characteristic of a glass, while the heat-treated sample (b) gives sharp peaks due to the presence of crystals. That is, this shows that a large amount of crystalline material is precipitated in the glass by the heat treatment. These peaks are due to fine crystals of fluoride solid solutions of PbF2, CdF2, YbF3, ErF3, etc. and it is calculated from the half value width thereof that the size of the fine crystals is very small. i.e. of the order of 20 nm.
- Fig. 3 shows transmission spectra of the glass sample before and after the heat treatment, in which the dotted line shows the result after the heat treatment and the solid line shows that before the heat treatment. It is apparent from this figure that the transmittance is hardly changed before and after the heat treatment. Generally, when foreign matter such as crystals are precipiated in a glass, the transmission is significantly lowered by scattering of light, but if the precipitated crystals are very small, e.g. smaller than the wavelength of light and the difference in refractive index between the fine crystals and matrix glass is small, the loss of transmission due to scattering of light can be so suppressed that it can be ignored. The result of Fig. 3 is the latter case.
- Fig. 4 shows the excitation power dependence of the visible light emission measured using the material according to Example 1 and a semiconductor laser of 980 nm as an excitation light source. All the emissions of 550 nm and 660 nm are due to the energy transition among a plurality of energy levels of rare earth ions (in this case, 4I 11/2. 4S 3/2 and 4F 9/2 levels of Er3+ and 2F 5/2 level of Yb3+ ), which shows the square dependence of the excitation power characteristic of the wavelength up-conversion.
- rare earth ions in this case, 4I 11/2. 4S 3/2 and 4F 9/2 levels of Er3+ and 2F 5/2 level of Yb3+
- a typical fluoride glass hitherto developed (35 % AlF3, 14 % YbF3, 1 % ErF3, 20 % PbF2, 5 % MgF2, 15 % CaF2, 10 % BaF2, mol %) was prepared using a platinum crucible in a nitrogen atmosphere. It has been confirmed that this glass is not stable because it contains no compound with strong bonding property, but has a high infrared-to-visible conversion efficiency with the same level as the fluoride single crystal.
- Fig. 1 (c) and Fig. 4 are respectively shown the emission spectra of the glass when this is irradiated by a semiconductor laser of 980 nm and the excitation power dependence of the emission intensity.
- the green emission intensity of the fluoride glass was about 1/2 as large as that of the transparent glass ceramic of Example 1 and the power dependences of both the glasses were substantially same. Thus, it was confirmed that the material of the present invention exhibited a higher efficiency over from a lower excitation power to a higher excitation light power than the fluoride glass.
- a transparent glass ceramic having a composition of 30 % SiO2, 15 % AlO 1.5 , 45 % PbF2, 10 % YbF3 and 0.1 % TmF3 (mol %) was prepared in an analogous manner to Example 1.
- this sample was irradiated by a laser of 980 nm, blue emission, one of the three primary colors, was strongly observed. This blue emission spectrum is shown in Fig. 5.
- Example 3-6 Samples of Examples 3-6 were prepared in an analogous manner to Example 1 and subjected to measurement of the infrared-to-visible wavelength conversion performance, e.g. the excitation power dependence S x of the visible light emission intensity when excited by a 980 nm laser, thus obtaining results as shown in Table 1 with the data of Examples 1 and 2.
- the infrared-to-visible wavelength conversion performance e.g. the excitation power dependence S x of the visible light emission intensity when excited by a 980 nm laser
- a transparent glass ceramic with a high infrared-to-visible conversion efficiency and high chemical, mechanical and thermal stability which can be applied to short wavelength solid lasers, full color displays, infrared light detecting sensors, etc.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Geochemistry & Mineralogy (AREA)
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21257293A JP3411067B2 (ja) | 1993-08-27 | 1993-08-27 | 波長上方変換透明化ガラスセラミックスおよびその製造方法 |
JP212572/93 | 1993-08-27 | ||
JP21257293 | 1993-08-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0640571A1 true EP0640571A1 (fr) | 1995-03-01 |
EP0640571B1 EP0640571B1 (fr) | 2001-10-17 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP94306307A Expired - Lifetime EP0640571B1 (fr) | 1993-08-27 | 1994-08-26 | Vitro-céramique transformant de longueur d'ondes de la lumière et son procédé de production |
Country Status (4)
Country | Link |
---|---|
US (2) | US5420080A (fr) |
EP (1) | EP0640571B1 (fr) |
JP (1) | JP3411067B2 (fr) |
DE (1) | DE69428651T2 (fr) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0716050A1 (fr) * | 1994-11-25 | 1996-06-12 | Corning Incorporated | Vitrocéramiques transparentes |
EP0739863A1 (fr) * | 1995-04-28 | 1996-10-30 | Corning Incorporated | Vitrocéramiques transparentes |
US5684815A (en) * | 1995-06-02 | 1997-11-04 | Central Glass Company, Limited | Upconversion laser material |
WO1998029351A1 (fr) * | 1997-01-02 | 1998-07-09 | Corning Incorporated | Composition vitroceramique transparente a base d'oxyde de fluor et procede de production associe |
EP0924171A1 (fr) * | 1997-12-22 | 1999-06-23 | Kabushiki Kaisha Ohara | Vitrocéramique luminescente |
WO1999047464A2 (fr) * | 1998-03-19 | 1999-09-23 | The University Of Leeds | Verre optique dope a l'erbium |
WO2000006510A1 (fr) * | 1998-07-27 | 2000-02-10 | Eugen Pavel | Vitroceramiques photosensibles fluorescentes et leur procede de production |
WO2000016169A1 (fr) * | 1998-09-10 | 2000-03-23 | Eugen Pavel | Dispositif, procede holographique de duplication de memoires holographiques et optiques, et copie de memoire ainsi obtenue |
US6132643A (en) * | 1998-01-06 | 2000-10-17 | Pavel; Eugen | Fluorescent photosensitive vitroceramics and process for the production thereof |
US6228787B1 (en) | 1998-07-27 | 2001-05-08 | Eugen Pavel | Fluorescent photosensitive glasses and process for the production thereof |
CN108409148A (zh) * | 2018-03-15 | 2018-08-17 | 杭州电子科技大学 | 红外非相干LED激发的上转换NaLuF4玻璃陶瓷及其制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113105113B (zh) * | 2021-04-09 | 2022-05-10 | 泰山学院 | 具有纯红光发光特性的特种光学玻璃及其制备方法和用途 |
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Cited By (21)
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EP0716050A1 (fr) * | 1994-11-25 | 1996-06-12 | Corning Incorporated | Vitrocéramiques transparentes |
CN1079783C (zh) * | 1994-11-25 | 2002-02-27 | 康宁股份有限公司 | 透明玻璃陶瓷和含有该玻璃陶瓷的光学纤维波导管 |
CN1047159C (zh) * | 1995-04-28 | 1999-12-08 | 康宁股份有限公司 | 透明玻璃陶瓷 |
EP0739863A1 (fr) * | 1995-04-28 | 1996-10-30 | Corning Incorporated | Vitrocéramiques transparentes |
AU696990B2 (en) * | 1995-04-28 | 1998-09-24 | Corning Incorporated | Transparent glass-ceramics |
US5684815A (en) * | 1995-06-02 | 1997-11-04 | Central Glass Company, Limited | Upconversion laser material |
GB2302442B (en) * | 1995-06-02 | 1999-09-22 | Central Glass Co Ltd | Upconversion laser material |
WO1998029351A1 (fr) * | 1997-01-02 | 1998-07-09 | Corning Incorporated | Composition vitroceramique transparente a base d'oxyde de fluor et procede de production associe |
US5955388A (en) * | 1997-01-02 | 1999-09-21 | Corning Incorporated | Transparent oxyflouride glass-ceramic composition and process of making |
AU731393B2 (en) * | 1997-01-02 | 2001-03-29 | Corning Incorporated | Transparent oxyfluoride glass-ceramic composition and process for making |
EP0924171A1 (fr) * | 1997-12-22 | 1999-06-23 | Kabushiki Kaisha Ohara | Vitrocéramique luminescente |
US6197710B1 (en) | 1997-12-22 | 2001-03-06 | Kabushiki Kaisha Ohara | Luminous glass ceramics |
US6204211B1 (en) | 1997-12-22 | 2001-03-20 | Kabushiki Kaisha Ohara | Luminous glass ceramics |
US6132643A (en) * | 1998-01-06 | 2000-10-17 | Pavel; Eugen | Fluorescent photosensitive vitroceramics and process for the production thereof |
WO1999047464A3 (fr) * | 1998-03-19 | 1999-11-04 | Univ Leeds | Verre optique dope a l'erbium |
WO1999047464A2 (fr) * | 1998-03-19 | 1999-09-23 | The University Of Leeds | Verre optique dope a l'erbium |
WO2000006510A1 (fr) * | 1998-07-27 | 2000-02-10 | Eugen Pavel | Vitroceramiques photosensibles fluorescentes et leur procede de production |
US6228787B1 (en) | 1998-07-27 | 2001-05-08 | Eugen Pavel | Fluorescent photosensitive glasses and process for the production thereof |
WO2000016169A1 (fr) * | 1998-09-10 | 2000-03-23 | Eugen Pavel | Dispositif, procede holographique de duplication de memoires holographiques et optiques, et copie de memoire ainsi obtenue |
CN108409148A (zh) * | 2018-03-15 | 2018-08-17 | 杭州电子科技大学 | 红外非相干LED激发的上转换NaLuF4玻璃陶瓷及其制备方法 |
CN108409148B (zh) * | 2018-03-15 | 2020-11-06 | 杭州电子科技大学 | 红外非相干LED激发的上转换NaLuF4玻璃陶瓷及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US5545595A (en) | 1996-08-13 |
JP3411067B2 (ja) | 2003-05-26 |
DE69428651D1 (de) | 2001-11-22 |
EP0640571B1 (fr) | 2001-10-17 |
JPH0769673A (ja) | 1995-03-14 |
US5420080A (en) | 1995-05-30 |
DE69428651T2 (de) | 2002-07-11 |
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